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Terpyridine complexes of Rhodium(I,III)

de Pater, B.C.

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Citation for published version (APA):de Pater, B. C. (2003). Terpyridine complexes of Rhodium(I,III). Amsterdam.

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Download date: 19 Feb 2020

Chapterr 5

Crystall Structure of the Novel Neutral Octahedral

Complexx [RhIII (Br)(Acetonyl)2(4,-(4^Butylphenyl)-

2,2:6\2M-Terpyridine)]. . Hokee C'. tie Pater.: Hans-VV. PYiihauf. ' Kee^ ('iuuhit/..' .Ian Praanje.'

Peterr H.M. Uiid/ekiar." Amnn \\ ' . CJaL! Kees Yr ie/e :

! i is i i : i !k '' i-.| M n k v n L r ( ' - ï a m ^ i n . I : n \ e i M : \ ,.[ Ai ikU'r . i . i : : . . \ k - u \ w VL-IIKT-.L-.I ;;,!:: I'if-. : i : | s. \ \ \ A m vie: J a m . 1 In.

N e l t v i L u i i K .. I . ; \ : ; I ^ ' ^ n - j ^ h . j S . j . e-m;m:- |n< | - ^ k . i k , \ U \ .1 r;|

] )c; i ;ni : ] \ . ' inn ;>: h M i ^ j ' k - C " i v im-a \ . ! 111 -. ei - i t \ o I \ ' i : i r ieei-r i . 'I i v n n > m \ e \ l I . ( ö 1^ h i ) W n v L e n . 1 he V i l i e i k i m

Abstract t

Inn the p i v \ i n i K chap ie i 'v we h a \ c dc - . cn l vd the s\ i i thc^cs. character isat ion, pi opert ies. r c a c t m n

ann J an app l i ca t ion u!' K in I.' i c r p \ n d i n c o 'n .nk ' \L ' s . Il u , b found that, once die neh l cond i t ions were

l l R ' 1 .. t h C O U l C O J ] ] C Ot l l ] L ' c h e m i s t T A o f t h e s e t l l ] | l p ] L \ L ' V C O l l l d I X ' p l ' e d i c ' . e d t O a C C [1 a I t ! d C i J t V C .

Se \e ra ll r hod ium o ' i i i | i k : \ c v containim, ' :nnh a terdcula le n i t roLvn imand and an organic L:roup

h o u n dd to the mcla i are k n o w n . Moweu ' r . r h o d i u m c o m p l e x e - ot Icrdcniu ic n i l i o - e n h^a i i ^^

s \n the -ess ot Rhi I i - tcrp\ n d i n e c o m p l e x e - i:i d i ü e i e n i o r^anm soKcn ts . we encountered one such

species.. I. pon s tand in^ at r o o m [cmpcraLi re . a m ix tu re i''l 4 ' - i 4 - / h u i \ l phcn \ I i-2.2 :ff.2' - !erp \ n Jute

A\IAA\IA \U\v. K n i ( ' ( ) l ) | in acetone u ; i ^ mund to deposit cr>staU o\' ' k h ' d R n ; acctonx I i_>4' (4

, ' h u i \ l | i h c n \ ]] i J.2 : n ' . 2 " - i e r | \ \ r i d i ! i e i | . Here we re pon the \ \ n thes i s and c h a r a c i e n v i l i on o f this

L incon in ionn comp lex .

!! K l

AA ? FH'^iU-c'^iCQionyrtzrp': complex

Introduction n

Y\\ e ha\ e svnthcsiscd se\ cral Rhi I i-tcrp\ i'i j i nc complexes in \ anous i n'L'ani*.' M)] \ cuts f c.t'.

Clmi'UrClmi'Ur 2 and .M. Reaction of 4 -i 4-/hut> Ipheiu I !-2.2':(i'.2"-lerp} ridine and | Htn Rni(..'()[') 11 in

iitiit clinic. how e\ er. imex peeled h produced (he Rhi III i complex [ Rh i Bm acetoiu I i i4'-< 4

/hui\ ]phci i \]] i-2.2":(Y.2"tcrp>ridmeil i 1 i. Based on cpwal lo^raph ic studies, mass measurements

11-us!! Atom Rom hardi l lent and Held Desorplion i and I) FT calculations, we lui\ e a clear insight in

itss structure and composit ion. Kach aceton\ I rjroup is a-bonded lo the Rh-metal of complex 1 in

axiall position relative to the plane of the Tp\: " li^and. 'I'his is the first w el I -characterised example ol'

aa lerdentaie nitrogen nieial com [ilex with two carbon aloms or-honded lo lli e metal atom.

Kxptrinuntall Section

.. 'I'he 4'-i4-/bul\ lphen\ 1 i-2.2':n .2 '-k'rp\ ridine (Tpv: ) lieand w as s\nthcsiscd and

pnril'iedd as described in Chapter Y '['he Rh-prccin'sor complex ! RlnRni ( ' ( ) [ ) 11_ (COD = 1.5-

c>cloocladiene.ii was s\nthesjsed as described in (."napu r 2. Acetone was treshK disiilled from

RR -().. Complex 1 was formed in acetone under an inert atmosphere i purit iecl ar^on i. iisim: standard

Schlenkk techniques. The formation ot' 1 was monilored wii h a 1'Y/YIS spectrometer. I'.leclronic

absorptionn spectra were recorded on a IIPS453 diode-arra\ spectrophotometer, last atom

bomhardnientt T A B ' ; mass spectromelrv was earned mil usin a JI.OL .IMS S \ / S \ ] O . V\ four-

sectorr mass speclroinetcr. coupled to a .IKOI. MS-7000 data system. The sample was loaded in a

matrixx phase i ylxcerol) on a stainless steel prohe and bombarded with xenon atoms w uh an enery\

o[o[ 3 KeY. DuriiiL. ' the h idi resolnlion I A B MS measLii'cments a resolving pnwcr o\ 5000 i }()',

\a l ie\\ defitiitioni was used. C\] ami glycerol were used lo calibrate the mass spectrometer. Field

Dcsorplionn i ld ) t mass spectrometry was carried out using a .IKOI. .IMS SX/S.Y 102.A four-sector

masss spectromclcr. coupled to a Jl,() l , MS-\ll ' l>U2 I i)/ l 'PI') s\siem program. 10 urn Tungsten wire

Id.")) emitters containing carbon microneedles with an average length ot' 3d u m were Used. The

samplee w as dissolved in ntelhanol/'w ater and then loaded onto an em i Her with lli e dipping or swinge

11 1 1

ChapterChapter 5

technique.. An emitter current of 30 mA was used to desorb the sample. The ionsource temperture

wass 50 C.

Atomm numbering of complex 1 is done according to the following scheme:

// X

Synthesis. .

15 5

N N

0---N N

Tiff f

[Rh11 (Br)(acetonyl)2(4'-(4-fbutylphenyI)-2,2,:6,,2"-terpyridine)] . 1

Acetonee (40 ml) was added to 0.023 g [RhBr(COD)|: (0.039 mmol) and

NN 0.029 g Tpy* (0.079 mmol). This mixture stood for a prolonged period

(severall weeks) at room temperature, without stirring. During this period, a

darkk blue reaction mixture was formed. Eventually, this mixture became

yellow,, yellow single crystals started to grow and were isolated from the

motherr liquor. After drying the product by removing the solvent under reduced pressure, complex 1

(yieldd -1009?) was collected as a yellow powder.

II ArTMS: m/: 604.03 [(M_)-CH :COCH :]: FD'MS: in/: 661.08 |M+].

Duee to the insolubility of complex 1 in various organic solvents, no NMR data could be generated.

Furthermore,, due to unknown reasons, elemental analysis gave no good results.

X-ra yy structur e determination of complex 1.

AA crystal with dimensions 0.13x0.20x0.23 mm approximately was used for data collection on an

Enraf-Noniuss CAD-4 diffractometer with graphite-monochromated CuKa radiation and w-20 scan.

AA total of 3272 unique reflections was measured within the range -14<h< 14. 0<k<28. 0<1<I 3. Of

these.. Z " ^ - were abu\ e 11 j c s i ^u ihcancc le \e l o] 4 G (1- . . i and were treated as observed. 1 he range

ui '' is i : i H) /. was ii.()44 -11/05 A i . v l K0' - -^4 .n ). [ n o reference re 11 cel ions 11 n 3 1 ]. [1

^^ f i were measured hour lv and showed U' < decrease dui"iii;j the t>4 h co l lec t ing urne. n h i c h n a s

corrce icdd 1'ur. L n i t - c c l l parameters were ref ined h\ a least-squares t i l t i ng procedure Using 23

ref lect ionss wi th 4<i.OS<ii<42.S!v (. 'orrecuoi is fur I .u reu l / and po lar isat ion c f fec ls were app l ied .

Abso rp t i onn eurreel io i i was per fo rmed w i ih the p rogram Pk A l ( ) \ . fo l low i n g ! he method o f No r th

ett a l . usmg T scans ui ' I n e ref lect ions, w i t h coef f ic ients ut t ik ' range 0.7S ! -0 /J55. The structure

wass s u l \ e d h\ dte R A T T Y op t ion o[' the I )IR1 )lk'0(J program s_wem. The aswumetnc uni t

conta inss hal l ' a molecule n i ih Rh. Br. V 2 i . C' iSj . ( ' A d . d . 1 2 i and C'i 1 " ! uu a special pos i t ion

(( 1 d .v . l t. \ f l e r isotropic re f inement a A f synthesis rexealed 4 peaks: these n c r e interpreted as i n u

moleculess acelouc n\' c r W a l l i s n i i o n w u h an occupancy factor 0.5. sharing their n i e l l n l groups:

co i i scquen thh (_'i2si and () i I s ! h a \ c an occupanc) factor 0.5. "["he a tomic d isplacement parameters

o!! the met In 1 groups o f ihe .'Bu u i o i e u n ere \ er\ high aiut it u as decided to d i \ idc ihcsc atoms in to

(>> ( ' -a toms w u h occupanc\ factor 0.5. The h u l r o g e n atoms were ca lcu la ted, except those lor the

soKcn tt molecu le and kepi f ixed at their ca lcu lated posi t ions w i t h I ' = 0.1 A" . k u l l - m a l r i x least-

squaress ref inement on 12 isotropic tor the d isordered ( ' -a lums ut' the f l ïu and the soKen l and

an isu i rop icc for the remainder o f (he atoms, c o m erged to R o.t.iod. R u n .o fó . ( \ n),. , = 0.02. S

0.S4.. A we igh t i ng scheme u [3(1 d.0] A a t f o b s i ) 0.01 <n( I 'ohs i f ] ' was used. The

seeondaiAA isotropic ex t inc t ion coef f ic ient ' ref ined to ("i = 330/ 23 i. A f inal d i f fe rence Courier map

re \ea ledd a residual e lectron den>it\ hemeen I A and 1.2 cA ' in ihe \ i c i n i t \ o f [he Rh. Scatter ing

factorss were taken f rom Orou ic i and M a n u . i i i ie i nat ional i'ahics \\>^ X r.i\ ( ' r \ s i a i ! o g r a p h \ . The

anomalouss scattering ot' Rh and Br was taken into accouu i . ' A l l ca lcu lat ions were per fo rmed n i lh

\ T . \ L 5 .. A ' unless stated. o therwise, f u r t h e r e n stal and ref inement daia are l isted m T i l hi e 5 . 1 . A

I 'L II "1 O N dran ing is show n in F igur e 5 .1 .

II a lik ' 5. t : 0 r w , : l .ma i .-r ri ieineiu U.u.i m: t i .mpk w 1.

I I

|-..r-m.;.; :: C t l I C \ I ) Kt i . C I ! i C( I

X I -- ' . ( - ! MS

C;-.-c JJ -,-,. L-:-, \ I , - i - . I :n .

ChapterChapter 5

Spacegroup p

a.a. A

b.b. A

c.c. A

(/... deg

(3.. deg

y.. deg

\.. \

F(000) )

7".. K

crvslall class

spacee group

i :: a

11.990(2) )

22.679(2) )

12.044(2) )

90 0

104.39(2) )

90 0

3172.3(8) )

1456 6

233 3

monoclini i

P22 in

/>/> . g/cm3

Figuree 5.1. PLUTON drawing with atom labelling for complex I

114 4

AA rare Rh(lll)-diacetonyl-terpy complex

Densityy functional theoretical (DFT) study of complex 1.

Forr obtaining a better insight in the geometrical conformation of complex 1. DFT calculations

weree performed for model complex lm (Figure 5.2) |Rh(Br)(-CH:COCH?)2(Tpy)| (Tpy =

2.2':6'.2"-terpyridine).. The atom labelling of lm is similar to complex 1. The TURBOMOLE

programm was tised for these calculations."' 2' using the BP86 functional.''"'" s an SV(P) basis set. a

medium-sizedd integration grid and the RI approximation."9' The structures of complex lm and its

ciscis isomer were optimized without constraints.

13 3

Figuree 5.2. Model complex lm.

UV-VI SS spectroscopy of complex 1.

Electronicc absorption spectra were recorded on a HP8453 diode-array spectrophotometer.

115 5

ChapterChapter 5

Results s

Formationn of [Rh III (Br)(acetonyl)2(4,-(4-/butylphenyl)-2,2':6',2"-terpyridine) J (11.

Afterr stirring at room temperature |Rh(Br)(COD)|: (COD = 1.5-cyclooctadiene) and 4'-(4-

?butylphenyl)-2.2':6'.2"-terpyridinee in acetone, a dark blue reaction mixture was formed. A UV-VI S

electronicc absorption spectrum of tlii s mixture (Figure 5.3) showed very similar absorption bands

inn (he visible region (metal-to-ligand and ligand-to-ligand charge transfers: MLCT and LLCT.

respectively)) as observed tor complex [Rh (Br)(2,2':6'.2"-terpyridine)| in EtOH ic.l'. Chapter 2).

Basedd on these similar electronic absorption spectra, il can be suggesied that the initially dark blue

colouredd reaction mixture in acetone contains the complex [Rh i Br)(Tp\ i].

4 , ,

3.55 -

33 -

2.55 -

<< 2 -

1.55 -

•• -I 0.55 -

00 -•

3400 440 541 640 740 840 940

Wavelengt hh (nm )

Figuree 5.3. UV/VIS absorption spectrum <-<\' [Rh (Br)(2.2':6',2"-lerpyridine)] in

acetonee (0.5s niMi. measured afterca. 5 minutes reaction time.

Uponn standing at room temperature, the blue reaction mixture slowl) becomes yellow and

yelloww crystals of complex 1 are growing. The formation of complex 1 (Scheme 5.1) is monitored

forr 24 hours ( I scan per hour) by UV/VI S spectroscopy (Figure 5.4). Complex 1 is air and

thermallyy stable, and is very poor soluble in organic solvents.

[Rhh (Br)(2,2':6',2"-terpyridine)|

11 16

AA rare Rh(lll)-diacetonyl-terpy complex

33 n

2.55 -

2 2

1.55 -

11 -

0.55 -

00 -350 350

Complexx 1

4000 450 500 500

b b

550 550

3400 440 540 640 740 840 940

Wavelengthh (nm)

Figuree 5.4. a) Selected electronic absorption spectra of the formation of complex 1 (0.55

iiiM )) for 24 hours; b) electronic absorption bands of 1 after ca. 60 hours standing at room

temperature. .

Inn F igure 5.4a. no isosbestic points can be observed, since complex 1 precipitates out of the

solution. .

[Rh(Br)(COD)]; ;

Schemee 5.1. The in sim formation of complex 1.

ii 17

St ruc tt ur e of e o m p k x 1: c r \ st a l lo y n i p h ic ;m d I) F T studies .

II he de ieH i . ina i io i - ot the ^eomet r iea l mr.:, >n;:aiion ot s i m p l e x 1 \ \ a ^ based or. \ - r a \ diMraeUon

Mudiess .siul l)|-"l ^Lik-iilalLoii-.. ko r die v i w a l l o ^ - a p h i e - Indies o l eonip lex 1. the \ e l l o u r r \ s t a l s

weree tint dr ied under \ a e u u u i . sjnee [tiv latter desiroved the e i x - t a k into J I H W ^ T . presumable

' veausee i-• 1 li'sv. ul ilk- aeeione o i ' - .u iu t i i i ' ! - . I ui die I )!•'[' ealeu kit ions, model ^-(tm]T 1 cx l m was Lts;.'J.

M o d e !! t i l l ha-- a l e k . l i v e k -ampk liLMhu OH npaied io e o n i p i e \ i . vdnie holh eo:up!e \es ^houk l

eonta i i ll \e ;> - nn i k i r eoo rd iua l i u i i sphere anuaid [he Ri l meta l . Neleeled hond lengths and angles ot

^ ' i n p k ' xx 1 and model 1m are i M e d in Tabl e 5.2 and 5.3 < [C^PCL ' I i \ o l \ .>.

"I"nl»li-- 5.2. N . 'Uva U»-,] :L- . ;- | , . • \ , ,:,o ..,,..!.•, , -; T ,• . a i r v x ^ 1 an J n r r^-.J.-i 1 in

khh H:

k rr \ l

k h - \ l l

k h - \\ ; •

Rii-C!! ^

\\ I

\\

\\ " \\ •

hn n A nn J

Hii k i

Bii K i :

vv kt

\ A k i : :

\

Rh-N N

(( 'J \

khh M

k i ,, \ i

i":i": \ .

\u\u ki

k!ii e n

i.1--

\: : M M

\ : : \ i i

-II 2

p .

•• ( ' -

tt :

<< ,-

aa ' i ,

(( '! -

(( ' ! 4

1 1

^ . " " '' -,i i u i ;

snn 4 ;

| f > < ! . > --

ii I : . M

ii I~ d •

:: r> dh

1 - . , , , . : :

ii !' ( i .4

ii

;; ; i ) i \< !

l l T l l

UL jj |

'.'. ~ s

Vll 1 h

I M . . ; ;

11 i .p l

i : "" i

i i ï

:: i ^ >

i :: s :

ii > . ;

v . -- ; <

"" i i

( ï >> s t a l k y rapine and 1)1-'T dal a s l in« dial d ie melh_\ lene earhon alnni of eaell aeeiotn 1 Liroup is

r rr bonded to die Rh melal ot eon ip lex 1. The u l i e r n a l n e interpretat ions w i th o w u e n aloms o f intael

ueetouee moleeu les eoord ina led in die melal eannoi he reconc i led n i d i (he o h s e n e d bond lengths. In

a d d i t i o n ,, coo rd ina t i on o f i w o aeeione molecules \ ia the H \ \ I ; U I I a ionis w o u l d result in a 2<)e-

!! IS

AA rare Rh(lll)-diacetonyl-terpy complex

configuration,, and is therefore unlikely. According to DI-T calculations, model 1m with the

acetonyll groups in cis position is 5.8 kJ/Mol higher in energ) than the trans analogue observed

experimentally. .

Withinn the crystals of complex 1, the shortest distance between the discrete monomers is 3.20 A.

Figuree 5.5 shows the packing in the unit cell, and Figure 5.6 illustrates the 7t-stacking interactions

betweenn the outer terpyridine pyridyl rings and the phenyl rings of neighbouring molecules.

4-4- - 2 rVV ?

ƒ// * \ \ * ** 4 , * »

** * *

JOTT f

r r I I

ÓÓ . . .

^N N

n-stackim m

*=4 *=4

—~~ N

I^W? ? « - - * • • $sr r tA A

7t-stacking g

Figuree 5.6. 7t-stacking interactions between neighbourii

moleculess of 1.

Figuree 5.5. Packing of complex 1.

11 19

Discussion n

S)) n t h e s K an d ^ n i \ s i n i i r r \ s t ; i l s ut 'comple x I .

I kk - \ : ; [ h , M - .«I , ; k ; k k 1 :- A M \ :....!,• , : . , ' \ p , M i k k k k i l - . • . : :>•; : . . ' I k - h:M ^ u r k k i k -

->> i . l k ' M ^ > •: ^ • ••: i, | 'v - \ I ,s k k :• ••: k .ak.k i • •" k k M.ak !>U.t- inka ; i k \ k i k \ Kh • Bt • I :n i • ( k.,".-, .' k .

'•>'•.. h k i i :- , > i r ; i : : : i \ \ ! k I V \ IS k k k ' k ' - ^ .:n in k . k k k k :. • i k ' !... . k - \ o ! ^ •. ••; 1. : k ; ikk k i h i k n

:<••:: I f i_ •••• k.-v h • i •; i i. s 111 > i i " I 1 l;-.'ii ; k ' m k n i i k u k k ' R k i - J n . i p\ k i i n k a f v ^>. '" ipk' \ I k s ^ : i MI

ii \ \ IS s [ V t I k w , . i ; p \ M k k s . M V I k k l ' k . I l n t , r n p L v . ' i k k k M l k k kM i l k ' h>! I l k k . M ; • ' ! O M l i p k A ] w ; | |

II i>r k k k v k h M i : ' \s [ , i is iM i:ic k k i \ I : ; M' u h k k :M i ;pk \ I. k a k k u t.n' \ k k n ik iks^ 's . k k k 'M

:;•.••;; k > sin : : v ikk^ i i ^ MI i i n \ ; n u I k ' KM / I M H S U : j K h ' H: a (' 'i >l) i : k sn i u n k ' in MkVkMk. w hi k i\-:c

II p\ I kk i iu l i- pi>ni'l\ s k u n k ' ;n j L L i » ik-j. W i l k a i : v i i rnn- j i k i ~i 11 N. i L - r - _ ilk1 kMinaii iM- ik k iM i ipkv I

p i i ' v W i l -- s . o k \ . k lnJ L i> s ink 11; I ; j h u \ i:; a k H M i k k k nunikM . I l n \u - \ kk il i n i k i l ; v ih; i ! u i!h l l n -

-AA luik---:'-. p u v k k n v s>nik' i m p i n i l k - k'! iui:-| v. I n k ; J V k ' s p i M k i h k k k :1k- pu .k k k i v r i k i l k k k s i s

(( 'h<ir; icH-ris;i l io n of ' u m i p k x I.

\ k i - -- l i k k i - u i c i l k ' k k ' I \ B ;if iJ I I )i a i k I k I N [ , J I : > - a r i a k k - . ip | v.rl i lk ' k >ni:.il k>n , m ! k k k k n v

"<< , 'M i ipk-x 1 ... . k p v k n l . „ I j o n r t ' 5 . 1 . ! k - ! ! . : - l l k a - a k k i k - k - . 'k :\M 1 k i i 1 a' : I V I !> k k,, su i a , , : k k .

: ' k k a k '' iha: ; \ \ . - , i k i . k \ ; j k k i p s k.- k k k k k [., i k ' I k : ü ia . , ; ,.; , . M i , p k \ I 11.MII V i a \ ;:iul I >l I

k i kk l - k >A ! I k l ! k M ' k I k > 'V v. > n Ü,! 1II. if U !!! •• •' ' : \ \ i V k . I . ' H I I ' N i •. ' !!k~ \\\' - ' k ' k n k k l ! k' t ' \ j ! k Jk ' i !

T l k k ' k k kk iiii.1 ni_>:k>;k: y r n u p - n: L n m p i , \ 1 j ; v r, l \>: ivk\l k •• dk ' Kh f i i r k i l u n h fhcn n k f l n k ' i k '

L'.ll 'bii if! nk >Mk.

II !k' h«Mkl kniL'l l i IvlWLk-n I k ' Kh i i k l k , : i \ l ( ' I '; n: ^nnipA'v 1 is ^ l L ii : \ h n k v " i ]i,!t J kk ' Kh ( '

k M l . l vv j ; , k :MV;p; ; r , ;hk ' R!: • 111 • k k h k i k i k - : ' k k C - , . M . | > \ \ . ' s J k s , : i | V l l P> i k . M i k / , , / . I l k '

i h t k ' i ^ i k k '' ui k ' i k l k'iiLMlls MI llk'sk' l v k k ' i l k l k l l k kMiripk'\L's ^uLikl ! \ ' L-;ii;si.\| in ,i J i i f o i v r . ! im'!^

k k v ll in hiMh s\sk ' i r is . hi k iM i ipk ' \ 1. ( ' I ; c \ JXTI-L'; kk's j cU'ccl I r om MI; a lk \ I k k k MI ; i !u in .

- i n k '' in o. MiipkAL'- i ' ! l lM.iri ikiM i l k ' L\Mi:p.i:ahiv.' t a'hi in a lum L 'Mkk i i in L's lhk i n . k ! ' \ \ k i \ k k v ; k

AA rare Fth(lll)-diacetonyl-terpy complex

effectt of a chloride atom. In addition, the acetonyl group, being formally a hetero-allyl group, ma)

showw some derealization, leading to a larger Rh-C distance.

oo o e

0 0

Soo far. the reaction mechanism for the formation o\' complex 1 from |Rh'(Br)(2.2':6'.2"-

terpyridine)]] in acetone is unknown.

Thee formation of square planar metal containing terdentate coordinated complexes with two

alky]] groups trans situated onto the metal centre is highly unusual. In the coordination chemistry of

terdentatee nitrogen ligands. the existence of related Rh-comple.xes with two carbon atoms c-bonded

too the metal centre is even unprecedented. The results described in this and other chapters

emphasisee the interesting properties of Rh(I)-terpyridine complexes.

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